Axel Horst

Estimating groundwater mixing and origin in an overexploited aquifer in Guanajuato, Mexico, using stable isotopes (strontium-87, carbon-13, deuterium and oxygen-18).

Stable Isotopes (strontium-87, deuterium and oxygen-18, carbon-13) have been used to reveal different sources of groundwater and mixing processes in the aquifer of the Silao-Romita Valley in the state of Guanajuato, Mexico. Calcite dissolution appeared to be the main process of strontium release leading to relatively equal 87Sr/86Sr ratios of 0.7042–0.7062 throughout the study area which could be confirmed by samples of carbonate rocks having similar Sr ratios (0.7041–0.7073). δ13C values (−11.91– −6.87‰ VPDB) of groundwaters confirmed the solution of carbonates but indicated furthermore influences of soil-CO2. Deuterium and 18O contents showed a relatively narrow range of−80.1– −70.0 ‰ VSMOW and−10.2– −8.8 ‰, VSMOW, respectively but are affected by evaporation and mixing processes. The use of δ13C together with 87Sr/86Sr revealed three possible sources: (i) carbonate–controlled waters showing generally higher Sr-concentrations, (ii) fissure waters with low–strontium contents and (iii) infiltrating water which is characterized by low δ13C and 87Sr/86Sr ratios. The third component is affected by evaporation processes taking place before and during infiltration which might be increased by extraction and reinfiltration (irrigation return flow).

Compound‐specific bromine isotope analysis of methyl bromide using gas chromatography hyphenated with inductively coupled plasma multiple‐collector mass spectrometry

Methyl bromide is the most important natural bromine contributor to stratospheric ozone depletion, yet there are still large uncertainties regarding quantification of its sources and sinks. The stable bromine isotope composition of CH(3)Br is potentially a powerful tool to apportion its sources and to study both its transport and its reactive fate. A novel compound-specific method to measure (81)Br/(79)Br isotope ratios in CH(3)Br using gas chromatography hyphenated with inductively coupled plasma multiple-collector mass spectrometry (GC/MCICPMS) was developed. Sample amounts of >40 ng could be measured with a precision of 0.1‰ (1σ, n = 3). The method results are reproducible over the long term as shown with 36 analyses acquired over 3 months, yielding a standard deviation (1σ) better than 0.4‰. This new method demonstrates for the first time Br isotope ratio determination in gaseous brominated samples. It is three orders of magnitude more sensitive than previously existing isotope ratio mass spectrometry methods for Br isotope determination of other organobromines, thus allowing applications towards ambient atmospheric samples.

Stable bromine isotopic composition of atmospheric CH3Br

Tropospheric methyl bromide (CH3Br) is the largest source of bromine to the stratosphere and plays an important role in ozone depletion. Here, the first stable bromine isotope composition (δ81Br) of atmospheric CH3Br is presented. The δ81Br of higher concentration Stockholm samples and free air subarctic Abisko samples suggest a source/background value of −0.04±0.28‰ ranging up to +1.75±0.12‰. The Stockholm δ81Br versus concentration relationship corresponds to an apparent isotope enrichment factor of −4.7±3.7‰, representing the combined reaction sink. This study demonstrates the scientific potential of atmospheric δ81Br measurements, which in the future may be combined with other isotope systems in a top-down inverse approach to further understand key source and sink processes of methyl bromide.

A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide*

A High-Volume Cryosampler and Sample Purification System for Bromine Isotope Studies of Methyl Bromide

Vapor Pressure Isotope Effects in Halogenated Organic Compounds and Alcohols Dissolved in Water

Volatilization causes changes in the isotopic composition of organic compounds as a result of different vapor pressures of molecules containing heavy and light isotopes. Both normal and inverse vapor pressure isotope effects (VPIE) have been observed, depending on molecular interactions in the liquid phase and the investigated element. Previous studies have focused mostly on pure compound volatilization or on compounds dissolved in organic liquids. Environmentally relevant scenarios, such as isotope fractionation during volatilization of organics from open water surfaces, have largely been neglected. In the current study, open-system volatilization experiments (focusing thereby on kinetic/-nonequilibrium effects) were carried out at ambient temperatures for trichloromethane, trichloroethene, trichlorofluoromethane, trichlorotrifluoroethane, methanol, and ethanol dissolved in water and, if not previously reported in the literature for these compounds, for volatilization from pure liquids. Stable carbon isotopic signatures were measured using continuous flow isotope ratio mass spectrometry. The results demonstrate that volatilization of the four halogenated compounds from water does not cause a measurable change in the carbon isotopic composition, whereas for pure-phase evaporation, significant inverse isotope effects are consistently observed (+0.3 ‰< ε < + 1.7 ‰). In contrast, methanol and ethanol showed normal isotope effects for evaporation of pure organic liquids (-3.9 ‰ and -1.9 ‰) and for volatilization of compounds dissolved in water (-4.4 ‰ and -2.9 ‰), respectively. This absence of measurable carbon isotope fractionation considerably facilitates the application of isotopic techniques for extraction of field samples and preconcentration of organohalogens-known to be important pollutants in groundwater and in the atmosphere.

Online isotope analysis of 37Cl/35Cl universally applied for semi-volatile organic compounds using GC-MC-ICPMS

Stable chlorine isotope analysis of organic compounds is potentially applicable in various fields in forensics and environmental analytics to investigate the fate of these substances in the environment, but a wider use of this technique is still hampered by the limited applicability of available offline and online techniques. In a previous study we presented a method for compound-specific chlorine isotope analysis of volatile organics including chlorinated methanes, ethanes and ethenes using gas chromatography interfaced with multiple-collector inductively coupled plasma mass spectrometry (GC-MC-ICPMS). In the current study we modified further the setup in order to extend the range of analytes towards semi-volatile organic substances with boiling points of up to 350 °C. The modified method was evaluated by using offline characterized in-house reference materials, such as chloroethenes, chloroacetic acid and hexachlorocyclohexenes. Additionally, analysis of various chlorinated benzenes, chlorinated phenols, chlordecone, dichlorodiphenyltrichloroethane (DDT) and related derivatives was demonstrated. The analytical precision (1σ) was usually better than ±0.2 mUr for single compound and ±0.3 mUr for compound-specific analysis of mixtures. Achieved accuracy was within ±0.2 mUr compared to available offline values. The isotopic detection limit could be significantly improved by one order of magnitude (250 pmol Cl on column, corresponding to ∼10 ng Cl) and is superior to other online state of the art approaches. The demonstrated method allows for the compound-specific stable chlorine isotope analysis of virtually all GC-compatible organics with versatility, high accuracy, and sensitivity.

Compound Specific Stable Chlorine Isotopic Analysis of Volatile Aliphatic Compounds Using Gas Chromatography Hyphenated with Multiple Collector Inductively Coupled Plasma Mass Spectrometry

Stable chlorine isotope analysis is increasingly used to characterize sources, transformation pathways, and sinks of organic aliphatic compounds, many of them being priority pollutants in groundwater and the atmosphere. A wider use of chlorine isotopes in environmental studies is still inhibited by limitations of the different analytical techniques such as high sample needs, offline preparation, confinement to few compounds and mediocre precision, respectively. Here we present a method for the δ37Cl determination in volatile aliphatic compounds using gas chromatography coupled with multiple-collector inductively coupled plasma mass spectrometry (GC-MC-ICPMS), which overcomes these limitations. The method was evaluated by using a suite of five previously offline characterized in-house standards and eight chlorinated methanes, ethanes, and ethenes. Other than in previous approaches using ICP methods for chlorine isotopes, isobaric interference of the 36ArH dimer with 37Cl was minimized by employing dry plasma conditions. Samples containing 2-3 nmol Cl injected on-column were sufficient to achieve a precision (σ) of 0.1 mUr (1 milliurey = 0.001 = 1‰) or better. Long-term reproducibility and accuracy was always better than 0.3 mUr if organics were analyzed in compound mixtures. Standardization is carried out by using a two-point calibration approach. Drift, even though very small in this study, is corrected by referencing versus an internal standard. The presented method offers a direct, universal, and compound-specific procedure to measure the δ37Cl of a wide array of organic compounds overcoming limitations of previous techniques with the benefits of high sensitivity and accuracy comparable to the best existing approaches.

Methyl chloride and methyl bromide emissions from baking: an unrecognized anthropogenic source

Methyl chloride and methyl bromide (CH3Cl and CH3Br) are the largest natural sources of chlorine and bromine, respectively, to the stratosphere, where they contribute to ozone depletion. We report the anthropogenic production of CH3Cl and CH3Br during breadbaking, and suggest this production is an abiotic process involving the methyl ester functional groups in pectin and lignin structural polymers of plant cells. Wide variations in baking styles allow only rough estimates of this flux of methyl halides on a global basis. A simple model suggests that CH3Br emissions from breadbaking likely peaked circa 1990 at approximately 200tonnes per year (about 0.3% of industrial production), prior to restrictions on the dough conditioner potassium bromate. In contrast, CH3Cl emissions from breadbaking may be of similar magnitude as acknowledged present-day CH3Cl industrial emissions. Because the mechanisms involve functional groups and compounds widely found in plant materials, this type of methyl halide production may occur in other cooking techniques as well.

Compound-Specific Stable Carbon Isotope Analysis of Chlorofluorocarbons in Groundwater

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), controlled substances due to their role in stratospheric ozone loss, also occur as dissolved contaminants in groundwaters. Stable carbon isotopic signatures may provide valuable new information on the fate of these compounds as has been seen for other priority hydrocarbon contaminants, but to date no method for extraction and isotopic analysis of dissolved CFCs from groundwaters has been developed. Here we describe a cryogenic purge and trap system coupled to continuous flow compound-specific stable carbon isotope analysis mass spectrometry for concentrations as low as 35 μg/L. The method is validated by comparing isotopic signatures from water extracted CFCs against a new suite of isotopic CFC standards. Fractionation of CFCs in volatilization experiments from pure-phase CFC-11 and CFC-113 resulted in enrichment factors (ε) of +1.7 ± 0.1‰ and +1.1 ± 0.1‰, respectively, indicating that such volatile loss, if significant, would produce a more (13)C depleted signature in the remaining CFCs. Importantly, no significant fractionation was observed during volatile extraction of dissolved CFCs from aqueous solutions. δ(13)C values for groundwaters from a CFC-contaminated site were, on average, more enriched than δ(13)C values for pure compounds. Such enriched δ(13)C values have been seen in other hydrocarbon contaminants such as chlorinated ethenes and ethanes due to in situ degradation, but definitive interpretation of such enriched signatures in field samples requires additional experiments to characterize fractionation of CFCs during biodegradation. The establishment of a robust and sensitive method of extraction and analysis, as described here, provides the foundation for such future directions.